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The structure 1 was obtained by static and dynamic computations based on the X-ray structure of its neutral complex precursor [Me2Si(C 5Me4)(μ-PCy)YCH2SiMe3] 2 and was confirmed to be a true active species for the polymerization of isoprene. See ref 7 for more details
-
2 and was confirmed to be a true active species for the polymerization of isoprene. See ref 7 for more details.
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56
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33846337302
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The data for isoprene insertion given here are for 4,3-insertion in the methyl-exo fashion. Isoprene 4,3-insertion in the methyl-enifo fashion also prefers a five-center TS pathway (see Supporting Information for more details). Because the 3,4-polyisoprene has been experimentally obtained in very high regioselectivity, the 1,4-insertion fashion was not considered in this work. An attempt to model the 3,4-insertion process finally led to the 1,4-insertion product, which was therefore not considered further. The coordination in a cis-fashion will not alter the reaction pathway.
-
The data for isoprene insertion given here are for 4,3-insertion in the methyl-exo fashion. Isoprene 4,3-insertion in the methyl-enifo fashion also prefers a five-center TS pathway (see Supporting Information for more details). Because the 3,4-polyisoprene has been experimentally obtained in very high regioselectivity, the 1,4-insertion fashion was not considered in this work. An attempt to model the 3,4-insertion process finally led to the 1,4-insertion product, which was therefore not considered further. The coordination in a cis-fashion will not alter the reaction pathway.
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57
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33846379755
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The slightly large variation trend in solvation energy may result from the fairly high polarity of the chlorobenzene solvent and the significant geometrical variation of the stationary points
-
The slightly large variation trend in solvation energy may result from the fairly high polarity of the chlorobenzene solvent and the significant geometrical variation of the stationary points.
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58
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33846393738
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4 and (P2)Me groups sterically inhibit the access of isoprene to Y2 from either the back-side or front-side.
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4 and (P2)Me groups sterically inhibit the access of isoprene to Y2 from either the back-side or front-side.
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59
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33846336289
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An attempt to locate a transition state to connect 3 and 3' was not successful. The reactants 2 and isoprene could be viewed to be in equilibrium with the π-complexes 3 and 3, Scheme 1
-
An attempt to locate a transition state to connect 3 and 3' was not successful. The reactants 2 and isoprene could be viewed to be in equilibrium with the π-complexes 3 and 3' (Scheme 1).
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60
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0037861823
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The lower stability (higher energy) of 4 than that of 3 might suggest that 4 is a highly reactive intermediate, which could subsequently undergo an energetically favorable isoprene insertion/ polymerization reaction. Such situations have been observed previously in other systems (e.g., Blok, A. N.; Budzelaar, P. H. M.; Gal, A. W. Organometallics 2003, 22, 2564-2570). However, further calculations on the reactions taking place at 4 are difficult because of the hugeness of the computational resources required for such a large system.
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The lower stability (higher energy) of 4 than that of 3 might suggest that 4 is a highly reactive intermediate, which could subsequently undergo an energetically favorable isoprene insertion/ polymerization reaction. Such situations have been observed previously in other systems (e.g., Blok, A. N.; Budzelaar, P. H. M.; Gal, A. W. Organometallics 2003, 22, 2564-2570). However, further calculations on the reactions taking place at 4 are difficult because of the hugeness of the computational resources required for such a large system.
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